Over the last two decades, the capacitive deionization (CDI) technique has been developed into a high performance, low-cost, and environmental-friendly desalination technology. The development of novel advanced nanostructures via the hybridization of diverse carbon materials to improve the performance of CDI technology has attracted considerable attention. In this study, the combination of graphene hydrogel and ZrO2-doped TiO2 nanofibers as efficient dopants into activated carbon (AC), has been achieved through a simple electrospinning technique followed by a post annealing process. The strong interactions between the graphene hydrogel, nanofibers and AC were found to enhance the wettability as well as the electrical conductivity of the AC. The morphology and electrochemical performance of the as-synthesized composite were characterized by fieldemission scanning electron microscopy (FE-SEM), Transmission electron microscopy (TEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). What's more, the X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and synchrotron X-ray absorption structures (XAS) are performed to investigate the atomic and electronic structure of titania and zirconia in order to understand their phase stability. We observed the appearance of anatase structure of titania and cubic structure of zirconia after doping the AC and graphene hydrogel with the nanofibers. The water contact angle of the composite was examined and found to be less than 3 degrees. The introduced nanocomposite showed high electrosorption capacity of 9.34 mg g(-1) at the initial solution conductivity of similar to 100 mu S cm(-1), which is much higher compared to the other surveyed materials; these results should be attributed to its significant hydrophilicity, high specific capacitance, and reduced charge transfer resistance.